CN110083010A - The manufacturing method of photosensitive polymer combination, photosensitive film, permanent resist and permanent resist - Google Patents

The manufacturing method of photosensitive polymer combination, photosensitive film, permanent resist and permanent resist Download PDF

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CN110083010A
CN110083010A CN201910193891.XA CN201910193891A CN110083010A CN 110083010 A CN110083010 A CN 110083010A CN 201910193891 A CN201910193891 A CN 201910193891A CN 110083010 A CN110083010 A CN 110083010A
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ingredient
polymer combination
photosensitive polymer
combination according
mass parts
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名越俊昌
田中惠生
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C08G59/186—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

Abstract

The present invention provides a kind of photosensitive polymer combination, the photosensitive film of the photosensitive polymer combination is used, the manufacturing method of permanent resist and permanent resist, the photosensitive polymer combination contains: (a) ingredient: sour modified epoxy, (b) ingredient: the photopolymerization monomer with ethylenically unsaturated groups, (c) ingredient: Photoepolymerizationinitiater initiater, (d) ingredient: epoxy resin, and (e) ingredient: inorganic filler, (a) ingredient contains sour modified bisphenol phenolic resin varnish type epoxy resin, and then condition as defined in meeting.

Description

Photosensitive polymer combination, photosensitive film, permanent resist and permanent resist Manufacturing method
The application be the applying date be August in 2012 9, application No. is points of 201280038974.8 patent application for China Case application.
Technical field
The present invention relates to the manufactures of photosensitive polymer combination, photosensitive film, permanent resist and permanent resist Method.More particularly, it relates to for manufacturing using in printed wiring board purposes, the permanent resist of conductor package substrate on the way Suitable photosensitive polymer combination.
Background technique
Densification along with the high performance of various electronic equipments, especially conductor package substrate is constantly being sent out Exhibition, the photosensitive solder resist (solder resist, below also referred to as permanent resist) used for outermost layer come It says, it is desirable that it is more than previous reliability that it, which has,.Specifically, with the high multiple stratification of substrate and the enlargement of chip, have disconnected The necessity for splitting patience increases, especially in temperature cycling test, it is desirable that having is more than previous fracture patience.
In addition, the imperceptibility of routing space is also developing along with densification, such as even if line width/it is divided into 8 μm/8 μm routing space below also requires electrical isolation patience.It is usually to carry out super add as the accelerated test of electrical isolation patience Fast life test (HAST).Super accelerated life test is to apply in the environment of 130 DEG C, 85%RH to 8 μm/8 μm of comb-type electrode Add assigned voltage and evaluates the very strict test of insulation patience.
In the past, as the solder resist of conductor package substrate purposes, always using for example containing making acrylic acid and first The addition of rank phenolic resin varnish type epoxy resin, the photonasty for then passing through the anhydride modified sour modified epoxy for capableing of alkali development Resin combination (see, for example patent document 1) and for the purpose of improving patience to TCT (temperature cycling test), into one Walk the photosensitive polymer combination (see, for example patent document 2) containing elastomer.
In addition, in recent years, in order to improve reflux patience (reflow resistance), using containing silica filler Photosensitive polymer combination (see, for example patent document 3), in order to improve HAST patience, using containing with specific structure The photosensitive polymer combination (see, for example patent document 4) of photopolymerizable compound.
Existing technical literature
Patent document 1: Japanese Unexamined Patent Application 61-243869 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2002-162738 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2011-13622 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2011-48313 bulletin
Summary of the invention
The problem to be solved in the present invention
But previous photosensitive polymer combination above-mentioned requirement high reliability use on the way, especially meeting In terms of being broken patience and HAST patience the two, there are also rooms for improvement.In addition, in order to meet high multilager base plate, jumbo chip Conductor package substrate used in solder resist fracture patience, need CTE (thermal expansion coefficient) low and Tg (glass Glass transition temperature) high photosensitive polymer combination, there are also rooms for improvement for previous photosensitive polymer combination.
Fracture patience in a kind of the object of the present invention is to provide CTE low, Tg high and high multilager base plate it is excellent and The excellent photosensitive polymer combination for capableing of alkali development of HAST patience under ultra tiny interval and the photonasty group is used Close the photosensitive film of object, the manufacturing method of permanent resist and permanent resist.
The means solved the problems, such as
First scheme of the invention is related to a kind of photosensitive polymer combination, contains: (a) ingredient: sour modified epoxy tree Rouge, (b) ingredient: photopolymerization monomer, (c) ingredient with ethylenically unsaturated groups: Photoepolymerizationinitiater initiater, (d) ingredient: ring Oxygen resin and (e) ingredient: inorganic filler, (a) ingredient contain sour modified bisphenol phenolic resin varnish type epoxy resin, in turn Meet at least one condition of following (I) and (II) expression.
(I) described (b) ingredient contains the photopolymerization monomer with tristane structure and urethane bond.
(II) 100 mass parts of total amount relative to (a) ingredient and (b) ingredient, (e) ingredient, which contains, to be had more than The maximum particle diameter of 60 mass parts is 1 μm of silica filler below.
The fracture patience that the photosensitive polymer combination can be used as in CTE low, Tg high and high multilager base plate is excellent The solder for capableing of alkali development that HAST patience under good and ultra tiny interval is excellent, clarity and gold-plated patience are excellent is against corrosion Agent utilizes.
The detailed reason that effect of the invention can be obtained is not clear, but for example it is contemplated that as follows.Make always in the past Sour modified epoxy is in terms of low CTEization and fracture resistance and insufficient in structure.It is thus regarded that by using With the sour modified bisphenol phenolic resin varnish type epoxy resin of both bis-phenol part and novolaks part in resin, resin it is rigid Property, crosslink density improve, can be realized low CTEization, and fracture resistance can be improved.And then speculate, by the way that above-mentioned acid is changed Property bis-phenol phenolic resin varnish type epoxy resin and most suitable ingredient are combined, and effect of the invention may be implemented.
In addition, average grain diameter and maximum particle diameter refer to using Microtrac method or the survey of Nanotrac method in this specification Fixed value.
Above-mentioned acid modified bisphenol phenolic resin varnish type epoxy resin, which preferably comprises, to be made multi-anhydride and carboxylate addition and obtains Sour modified bisphenol phenolic resin varnish type epoxy resin, the carboxylate be have the following general formula (1) indicate structure asphalt mixtures modified by epoxy resin The carboxylate that rouge is formed with the monocarboxylic acid containing ethylenically unsaturated groups.
[in formula (1), R1Indicate hydrogen atom or glycidyl, R2Indicate that hydrogen atom or methyl, n indicate 1 or more.In addition, Multiple R1And R2Respectively it may be the same or different.]
In addition, the above-mentioned photopolymerization monomer with tristane structure and urethane bond is preferably comprised with following The photopolymerization monomer for the part-structure that general formula (2) or general formula (3) indicate.It is possible thereby to further increase Tg and resistance to HAST.
[in formula (2) or formula (3), R3、R4、R5And R6Indicate Direct Bonding, alkylidene or arlydene.]
In addition, above-mentioned (b) ingredient preferably comprises carbamate compounds, the carbamate compounds are to make to have Diol compound, diisocyanate cpd and the compound with ethylenically unsaturated groups and hydroxyl of tristane structure Obtained from reaction.
In addition, above-mentioned photosensitive polymer combination preferably further contains curing accelerator in the molecule with amino. Thus, it is possible to further increase the adaptation with thin copper film.
Alternative plan of the invention is related to a kind of photosensitive film, has supporter and is set on the supporter Photosensitive layer, the photosensitive layer are made of above-mentioned photosensitive polymer combination.
Third program of the invention is related to a kind of manufacturing method of permanent resist, has following processes: on substrate The process for the photosensitive layer being made of above-mentioned photosensitive polymer combination is set, active ray is irradiated with pattern-like to the photosensitive layer Process and so that the photosensitive layer is developed and the process that forms permanent resist.
Fourth program of the invention is related to a kind of permanent resist, by the solidfied material of above-mentioned photosensitive polymer combination It constitutes.In addition, permanent resist of the invention can be by keeping photosensitive polymer combination of the invention solid using light and/or heat Change and obtains.As a result, in above-mentioned solidfied material, the reactive group of above-mentioned photosensitive polymer combination because of light and/or heat cure, Part or all is disappeared by reaction.
The effect of invention
Above scheme according to the present invention, being capable of providing one kind can be with alkali development and CTE is low, Tg high and takes into account height The photosensitive polymer combination of the HAST patience under fracture patience and ultra tiny interval in multilager base plate and the sense is used The manufacturing method of the photosensitive film of photosensitive resin composition, permanent resist and permanent resist.
Detailed description of the invention
Fig. 1 is the schematic section of conductor package substrate.
Fig. 2 is the schematic section of flip-chip type package substrate.
Specific embodiment
In the following, the preferred embodiments of the present invention is described in detail.
[photosensitive polymer combination]
Photosensitive polymer combination of the invention is following photosensitive polymer combination: it contains (a) ingredient: acid is modified Epoxy resin, (b) ingredient: photopolymerization monomer, (c) ingredient with ethylenically unsaturated groups: Photoepolymerizationinitiater initiater, (d) Ingredient: epoxy resin and (e) ingredient: inorganic filler, above-mentioned (a) ingredient contain sour modified bisphenol nobolak type epoxy tree Rouge, and then meet at least one condition of following (I) and (II) expression.
(I) described (b) ingredient contains the photopolymerization monomer with tristane structure and urethane bond.
(II) 100 mass parts of total amount relative to (a) ingredient and (b) ingredient, (e) ingredient, which contains, has more than 60 mass parts Maximum particle diameter be 1 μm of silica filler below.
In the following, each ingredient is described in detail.
[(a) ingredient: sour modified epoxy]
Photosensitive polymer combination of the invention contains sour modified epoxy and is used as (a) ingredient.Above-mentioned acid modified epoxy Resin can for example be obtained and making multi-anhydride (a3) with carboxylate addition, which is epoxy resin (a1) and contain The carboxylate that the monocarboxylic acid (a2) of ethylenically unsaturated groups is formed.
Above-mentioned acid modified epoxy can be obtained by the reaction in two following stages.Initial reaction (with Under be easily known as " first reaction ") in, the epoxy group of epoxy resin (a1) and the monocarboxylic acid containing ethylenically unsaturated groups (a2) carboxyl reaction, generates hydroxyl.In next reaction (being easily known as " the second reaction " below), thus it is speculated that be first Hydroxyl possessed by the hydroxyl and/or epoxy resin (a1) generated in reaction is original is reacted with the anhydride group of multi-anhydride (a3).
As above-mentioned epoxy resin (a1), as long as the compound of the epoxy group with 1 or 2 or more, just without spy It does not limit, such as phenolic resin varnish type epoxy resin, triphenol methane type epoxy resin, bisphenol A type epoxy resin, double can be enumerated Phenol F type epoxy resin, bisphenol-s epoxy resin, biphenyl type epoxy resin, bis-phenol phenolic resin varnish type epoxy resin.
As the above-mentioned monocarboxylic acid (a2) containing ethylenically unsaturated groups, can enumerate such as (methyl) acrylic acid, Crotonic acid, cinnamic acid.In addition, the monocarboxylic acid (a2) containing ethylenically unsaturated groups is also possible to multi-anhydride and has hydroxyl The half ester compound that is formed of (methyl) acrylate compounds or binary acid and unsaturated list glycidyl compound formed Half ester compound.Half ester compound refers to the chemical combination after the only one carboxyl of the compound for example with 2 carboxyls is esterified Object.As the half ester reactant, such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, horse can be enumerated Come the acid anhydrides such as sour, succinic acid and (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, three (hydroxyethyl) isocyanides Urea acid esters two (methyl) acrylate, glycidyl (meth) acrylate etc. are by conventional method according to equimolar than reacting Obtained from product etc..
Monocarboxylic acid (a2) containing ethylenically unsaturated groups can be used alone or two kinds of combination of the above use.Contain In the monocarboxylic acid (a2) of ethylenically unsaturated groups, preferred (methyl) acrylic acid.In addition, (methyl) acrylic refers to acrylic acid Base or methacrylic acid group, other similar performances such as (methyl) acrylate are also same.
Above-mentioned (methyl) acrylate with hydroxyl can enumerate such as (methyl) Hydroxyethyl Acrylate, (methyl) Hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, polyethyleneglycol (methyl) acrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate and dipentaerythritol six (methyl) acrylate.
As multi-anhydride (a3), such as succinic anhydride, maleic anhydride, tetrabydrophthalic anhydride, neighbour can be enumerated Phthalate anhydride, methyl tetrahydrophthalic anhydride, ethyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl six Hydrogen phthalic anhydride, ethyl hexahydrophthalic anhydride, itaconic anhydride and trimellitic anhydride.
In the first reaction, the ratio of the monocarboxylic acid (a2) containing ethylenically unsaturated groups is, relative to epoxy resin (a1) 1 equivalent of epoxy group, preferably 0.7~1.05 equivalent, more preferably 0.8~1.0 equivalent.
Epoxy resin (a1) and the monocarboxylic acid (a2) containing ethylenically unsaturated groups can be made to be dissolved in organic solvent To react.As organic solvent, the virtues such as the ketone such as methyl ethyl ketone, cyclohexanone, toluene, dimethylbenzene, durol can be used Fragrant race's hydro carbons；Methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol The glycol ethers such as single ethylether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether；Ethyl acetate, butyl acetate, butyl are molten The esters such as fine agent acetic acid esters, carbitol acetate；The aliphatic hydrocarbons such as octane, decane；Petroleum ether, naphtha, hydrogenated naphtha, The petroleum series solvent such as solvent naphtha.
In the second reaction, thus it is speculated that possessed by original in the hydroxyl and epoxide (a1) generated in the first reaction Hydroxyl occurs half ester with the anhydride group of multi-anhydride (a3) and reacts.Here, relative to the hydroxyl in the resin obtained by the first reaction 1 equivalent of base can be such that the multi-anhydride (a3) of 0.1~1.0 equivalent reacts.By the way that the amount of multi-anhydride (a3) is adjusted to the model In enclosing, the acid value of adjustable (a) ingredient.
(a) acid value of ingredient is preferably 20~180mgKOH/g, more preferably 30~150mgKOH/g, and particularly preferably 40 ~120mgKOH/g, extremely preferred is 50~90mgKOH/g.Development of the photosensitive polymer combination in aqueous alkali as a result, Property become good, excellent clarity can be obtained.In addition, the determination condition of acid value is identical as embodiment in this specification.
In addition, the weight average molecular weight of (a) ingredient is preferably 2000~30000, more preferably from the viewpoint ingredient for applying film property 3000~20000, particularly preferably 5000~15000.The different resin combination of molecular weight of more than two kinds can also be used. In addition, the determination condition of weight average molecular weight is identical as embodiment in this specification.
In addition, such as phenol novolak type acid modified epoxy acrylic acid can be enumerated as sour modified epoxy Ester, bisphenol-f type acid modified epoxy acrylic ester, urethane-modified bisphenol A-type acid modified epoxy acrylic ester.First rank phenolic aldehyde Varnish type acid modified epoxy acrylic ester for example can be obtained commercially EXP-2810 (Dainippon Ink Chemicals's system), bisphenol-f type acid Modified epoxy acrylic ester can be obtained commercially ZFR-1158 (Nippon Kayaku K. K's system), urethane-modified double Phenol A type acid modified epoxy acrylic ester can commercially obtain UXE-3024 (Nippon Kayaku K. K's system).
(a) ingredient contains sour modified bisphenol phenolic resin varnish type epoxy resin.As above-mentioned sour modified bisphenol phenolic varnish type Epoxy resin can be used without particular limitation.Bis-phenol structure in above-mentioned acid modified bisphenol phenolic resin varnish type epoxy resin can To be structure of bisphenol A, it is also possible to Bisphenol F structure, but from the viewpoint of fracture resistance is excellent, preferably sour modified bisphenol F Phenolic resin varnish type epoxy resin.
Specifically it is preferable to use make multi-anhydride (a3) and carboxylate for above-mentioned acid modified bisphenol phenolic resin varnish type epoxy resin Acid modified bisphenol phenolic resin varnish type epoxy resin obtained from addition, the carboxylate are the structures that there is following formula (1) to indicate Epoxy resin with containing ethylenically unsaturated groups monocarboxylic acid (a2) formed carboxylate.
[in formula (1), R1Indicate hydrogen atom or glycidyl, R2Indicate that hydrogen atom or methyl, n indicate 1 or more.In addition, Multiple R1And R2Respectively it may be the same or different.]
Above-mentioned n indicates integer value in single molecule, if it is the aggregate as different kinds of molecules, then it represents that average value Rational.
As above-mentioned sour modified bisphenol phenolic resin varnish type epoxy resin, commercially available product can be used.Such as Bisphenol F The EXP-3133 and EXP-3135 (being Dainippon Ink Chemicals's system) and EXP-2827 of phenolic varnish type acid modified epoxy (Dainippon Ink Chemicals's system).
[(b) ingredient: the photopolymerization monomer with ethylenically unsaturated groups]
Photosensitive polymer combination of the invention contains the photopolymerization monomer with ethylenically unsaturated groups.Wherein, From the viewpoint of resistance to HAST is excellent, the optical polymerism list with tristane structure and urethane bond is preferably comprised Body.At this point, preferably comprising the photopolymerization monomer of the part-structure with following general formulas (2) or general formula (3) expression.In addition, Tristane structure refers to for example containing structure represented by the following general formula (4).
[in formula (2) or formula (3), R3、R4、R5And R6Indicate Direct Bonding, alkylidene or arlydene.]
As above-mentioned alkylidene, preferably carbon atom number is 2~20 alkylidene, and more preferably carbon atom number is 2~10 Alkylidene, further preferably carbon atom number be 2~6 alkylidene.
The alkylidene for being 2~6 as above-mentioned carbon atom number, can enumerate ethylidene, propylidene, isopropylidene, Aden Base, pentylidene, hexylidene etc., but from the viewpoint of clarity, resistance to plating, preferably ethylidene or isopropylidene, it is more excellent It is selected as ethylidene.
As above-mentioned arlydene, preferably carbon atom number is 6~14 arlydene, and more preferably carbon atom number is 6~10 Arlydene.As such arlydene, phenylene, naphthylene etc. can be enumerated.
The above-mentioned photopolymerization monomer with tristane structure and urethane bond preferably makes (b1) to have tricyclic The change of the diol compound of decane structure, (b2) diisocyanate cpd and (b3) with ethylenically unsaturated groups and hydroxyl Close carbamate compounds obtained from object reaction.
There is the diol compound of tristane structure as above-mentioned (b1), such as tristane diformazan can be enumerated Alcohol.
It as above-mentioned (b2) diisocyanate cpd, is not particularly limited, but preferably with the compound of ring structure.Its In, it is more preferable from the viewpoint of resistance to fracture (heat resistance) that isophorone diisocyanate etc., which has the compound of rigid structure, 's.
In addition, above-mentioned (b3) has the compound of ethylenically unsaturated groups and hydroxyl from the viewpoint of crosslink density Preferably with the compound of 2 ethylenically unsaturated groups, more preferably with the chemical combination of 3 ethylenically unsaturated groups Object.As the compound in the molecule with 3 ethylenically unsaturated groups, can enumerate for example by the following general formula (5) table The compound shown.
[in formula (5), multiple R7And R8It respectively may be the same or different, R7Indicate that carbon atom number is 1~10 Alkylidene or carbon atom number be 6~14 arlydene, R8Indicate hydrogen atom, the alkyl or carbon atom that carbon atom number is 1~10 The aryl that number is 6~14, l, m and n indicate 1~10.]
L, m and n in above-mentioned formula (5) indicate the structural unit number of structural unit.Therefore, it is indicated in single molecule Integer value, if it is the aggregate as different kinds of molecules, then it represents that the rational of average value.
When the above-mentioned photopolymerization monomer with tristane structure and urethane bond be among the above, above-mentioned (b2) Diisocyanate is isophorone diisocyanate, the above-mentioned compound with ethylenically unsaturated groups and hydroxyl is above-mentioned logical It is preferred when compound represented by formula (5).As this compound, can commercially obtain UX-5002D-M20, UX-5002D-P20 (Nippon Kayaku K. K's system) etc..
In addition, (b) total amount 100 mass parts of the content of ingredient relative to (a) ingredient and (b) ingredient, preferably 10 mass Part~60 mass parts, more preferably 15 mass parts~50 mass parts.If (b) ingredient is lower than 10 mass parts, it is resistance to improve HAST Property effect become smaller, if it exceeds 60 mass parts, then have the tendency that development residue occurs.In addition, working as photosensitive polymer combination When containing (a) of more than two kinds ingredient, (b) total amount 100 mass parts of the content of ingredient relative to sour modified epoxy, also excellent It is selected as 10 mass parts~60 mass parts.
In addition, above-mentioned photosensitive polymer combination can be with no particular limitation further containing other optical polymerism lists Body, but the photo polymerization monomer preferably containing the ethylenically unsaturated groups with 3 or more.
As it is above-mentioned have 3 or more ethylenically unsaturated groups photo polymerization monomer, can enumerate for example make α, Beta-unsaturated carboxylic acid and trimethylolpropane tris (methyl) acrylate, tetramethylol methane three (methyl) acrylate, four hydroxyls Methylmethane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylic acid Compound obtained from the polyol reactions such as ester；Make three propylene of α, beta-unsaturated carboxylic acid and trihydroxymethylpropanyltri diglycidyl ether Compound obtained from the compound addition containing glycidyl such as acid esters.
Among the above, it from the viewpoint of fracture patience when further increasing reflux actual installation, preferably comprises from having (methyl) acrylate compounds of skeleton from pentaerythrite, (methyl) propylene with the skeleton from dipentaerythritol At least 1 selected in ester compound and (methyl) acrylate compounds with the skeleton from trimethylolpropane Kind, further preferably from (methyl) acrylate compounds with the skeleton from dipentaerythritol and with from three hydroxyls Selected in (methyl) acrylate compounds of the skeleton of methylpropane it is at least one kind of, further preferably have come from two (methyl) acrylate compounds of the skeleton of pentaerythrite.
Here, (methyl) acrylate with the skeleton from dipentaerythritol refers to dipentaerythritol and (methyl) third The carboxylate that olefin(e) acid is formed, the carboxylate further include with the modified compound of alkylene oxygroup.Preferably one point of above-mentioned carboxylate The quantity of ester bond in son is 6, but the compound that the quantity that can also be mixed with ester bond is 1~5.
Above-mentioned (methyl) acrylate compounds with the skeleton from dipentaerythritol can be obtained commercially KAYARAD DPHA、KAYARAD D-310、KAYARAD D-330、KAYARAD DPCA-20、30、KAYARAD DPCA-60、 120 (being Japanese chemical drug corporation).
In addition, above-mentioned photosensitive polymer combination preferably comprises the photo polymerization monomer with 2 ethylenically unsaturated groups.
As the above-mentioned photo polymerization monomer with 2 ethylenically unsaturated groups, can enumerate for example makes α, β-insatiable hunger With carboxylic acid and bisphenol-A system (methyl) acrylate compounds, dihydroxymethyl tristane two (methyl) acrylate, tristane Compound, two (first of carbamate obtained from glycol two (methyl) acrylate, the compound reaction containing glycidyl Base) acrylate compounds.They may be used alone, two or more kinds can also be used in combination.
Among the above, from the viewpoint of the heat resistance for improving cured film, two (first of dihydroxymethyl tristane is preferably comprised Base) acrylate or tristane glycol two (methyl) acrylate.Tristane diol dimethacrylate can be from quotient NK Ester DCP (village Xin Zhong chemical industry Co. Ltd. system) is obtained in industry, Tricyclodecane Dimethanol diacrylate can be from Commercially obtain NK Ester A-DCP (village Xin Zhong chemical industry Co. Ltd. system).
In addition, among the above, at the excellent aspect of clarity, preferably comprising bisphenol-A system (methyl) acrylate compounds.Bis-phenol In A system (methyl) acrylate compounds, 2,2- bis- (4- (five ethyoxyl of methacryloxy) phenyl) propane can be from quotient FA-321M (Hitachi's chemical conversion industry corporation) or BPE-500 (chemical industrial company, the village Xin Zhong system), 2,2- bis- (4- are obtained in industry (15 ethyoxyl of methacryloxy) phenyl) can commercially obtaining such as BPE-1300, (village Xin Zhong chemical industry is public Department's system).
[(c) ingredient: Photoepolymerizationinitiater initiater]
Photosensitive polymer combination of the invention contains Photoepolymerizationinitiater initiater.As optical polymerism initiator, as long as being suitble to It in the optical wavelength of used exposure machine, is just not particularly limited, well known optical polymerism initiator can be used.Specifically may be used To enumerate such as benzophenone, N, tetraalkyl -4 N ' -, 4 '-diaminobenzophenones, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butanone-1,2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholino-acetone-1,4,4 '-bis- (diformazans Base amino) benzophenone (Michler's keton), 4,4 '-bis- (diethylamino) benzophenone, 4- methoxyl group -4 '-dimethylamino two The aromatic ketones such as Benzophenone；The quinones such as alkyl-anthraquinone, phenanthrenequione；The benzoins compounds such as benzoin, alkyl benzoin；Benzoin alkane The benzoin ethers compounds such as base ether, benzoin phenyl ether；The benzil derivatives such as benzil dimethyl ketal；2- (adjacent chlorobenzene Base) -4,5- diphenyl-imidazole dimer, 2- (Chloro-O-Phenyl)-(m-methoxyphenyl) imidazoles of 4,5- bis- dimer, 2- (adjacent fluorine Phenyl) -4,5- diphenyl-imidazole dimer, 2- (o-methoxyphenyl) -4,5- diphenyl-imidazole dimer, 2,4- bis- is (to first Phenyl) -5- phenylimidazole dimer, 2- (2,4- Dimethoxyphenyl) -4,5- diphenyl-imidazole dimer etc. 2,4,5- Triarylimidazoles dimer；N-phenylglycine, N-phenylglycine derivative；Bis- (9, the 9 '-acridines of 9- phenylacridine, 1,7- Base) acridine derivatives, 1,2- acetyl caproyl such as heptane, 1- [4- (thiophenyl)-, 2- (O- benzoyl oxime)], ethyl ketone, 1- [9- ethyl- 6- (2- methyl benzoyl) -9H- carbazole -3- base] -, the oximes esters such as 1- (O- acetyl oxime)；7- diethylamino -4- methyl is fragrant The coumarin series compounds such as legumin；The thioxanthones based compound such as 2,4- diethyl thioxanthones；2,4,6- trimethylbenzoyls-two Acylphosphine oxide compounds such as phenyl-phosphine oxide etc..They can be used alone or two kinds of combination of the above use.
Among the above, it is preferable to use aromatic ketone, oxime ester from the viewpoint of obtaining the pattern form of clarity and rectangle Compound, thioxanthone compounds or acylphosphine oxide compound more preferably use aromatic ketone or thioxanthone compounds, further Aromatic ketone and thioxanthone compounds is preferably used in combination.
As above-mentioned aromatic ketone, most preferably 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholino-acetone-1.2- first Base -1- [4- (methyl mercapto) phenyl] -2- morpholino-acetone -1 can commercially obtain (the BASF plants of formula meetings of IRGACURE 907 Society's system).
As the above-mentioned compound with oxime ester, such as (2- (acetoxyl group imines ylmethyl) thioxanthene -9- can be enumerated Ketone), (1,2- acetyl caproyl, 1- [4- (thiophenyl) -, 2- (O- benzoyl oxime)], ethyl ketone, 1- [9- ethyl -6- (2- toluyl Base) -9H- carbazole -3- base] -, 1- (O- acetyl oxime)), wherein most preferably ethyl ketone, 1- [9- ethyl -6- (2- toluyl Base) -9H- carbazole -3- base] -, 1- (O- acetyl oxime)).This can commercially obtain IRGACURE-OXE02 (BASF plants of formula meetings Society's system).
As above-mentioned thioxanthone compounds, most preferably 2,4- diethyl thioxanthone.It can commercially be obtained KAYACURE-DETX-S (Nippon Kayaku K. K's system).
As above-mentioned acylphosphine oxide compound, most preferably 2,4,6- trimethylbenzoy-diphenies-phosphine oxide.This LUCIRIN-TPO (BASF Co. Ltd. system) can commercially be obtained.
, it is preferable to use phosphine oxide system Photoepolymerizationinitiater initiater from the viewpoint of making resist shape become more good.Make For this compound, such as 2 can be enumerated, the monoacylphosphine oxides such as 4,6- trimethylbenzoy-diphenies-phosphine oxide, Bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides, bis- (2,6- Dimethoxybenzoyls) -2,4,4- trimethyls-penta Double acylphosphine oxides such as base phosphine oxide.2,4,6- trimethylbenzoy-diphenies-phosphine oxide for example can be obtained commercially DAROCURE-TPO (CibaJapan corporation), bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides for example can be from Commercially obtain IRGACURE-819 (CibaJapan corporation).
In addition, preferably further containing the compound with acridine ring, the chemical combination with oxime ester to improve sensitivity Object, they also can be used together.
As the above-mentioned compound with acridine ring, such as 9- phenylacridine, 9-aminoacridine, 9- amyl can be enumerated Bis- (9- acridinyl) ethane of aminacrine, 1,2-, bis- (9- acridinyl) propane of 1,3-, Isosorbide-5-Nitrae-bis- (9- acridinyl) butane, 1,5- Bis- (9- acridinyl) hexanes of bis- (9- acridinyl) pentanes, 1,6-, bis- (9- acridinyl) heptane of 1,7-, 1,8- bis- (9- acridinyls) are pungent Bis- (9- acridinyl) nonanes of alkane, 1,9-, bis- (9- acridinyl) decane of 1,10-, bis- (9- acridinyl) hendecanes of 1,11-, 1,12- are bis- Bis- (9- acridinyl) alkanes such as (9- acridinyl) dodecane, 9- phenylacridine, 9- pyridyl group acridine, 9- pyrazinyl acridine, 9- are mono- Bis- (9- the acridinyl) -2- thiiranes of bis- (9- the acridinyl) -2- oxa- propane of pentyl amino acridine, 1,3-, 1,3-, 1,5- are bis- (9- acridinyl) -3- thia pentane etc., wherein bis- (9- acridinyl) heptane of preferably 1,7-.1,7- bis- (9- acridinyl) heptane examples It such as can commercially obtain N-1717 (Asahi Denka Co., Ltd.'s system).
(c) content of ingredient is that 100 mass parts of total amount relative to (a) ingredient He (b) ingredient are preferably 0.1 mass parts ~10 mass parts, more preferably 0.5 mass parts~7 mass parts.
The content of above-mentioned aromatic ketone is that 100 mass parts of total amount relative to (a) ingredient He (b) ingredient are preferably 0.1 matter Measure part~5 mass parts, more preferably 0.5 mass parts~5 mass parts, further preferably 1.0 mass parts~5 mass parts.
The content of above-mentioned thioxanthone compounds is that 100 mass parts of total amount relative to (a) ingredient He (b) ingredient are preferably 0.01 mass parts~1 mass parts, more preferably 0.05 mass parts~0.5 mass parts, further preferably 0.1 mass parts~0.3 Mass parts.
[(d) ingredient: epoxy resin]
Photosensitive polymer combination of the invention contains epoxy resin (wherein except above-mentioned sour modified epoxy).Make For (d), it is double that the bisphenol A type epoxy resin such as bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether etc. can be enumerated The biphenyl phenolic such as bisphenol-s epoxy resins, the xenol diglycidyl ethers such as phenol F type epoxy resin, bisphenol-S diglycidyl ether The hydrogen such as union IIs toluene phenol-type epoxy resin, the hydrogenated bisphenol A glycidol ethers such as epoxy resin, union II cresols diglycidyl ether Change bisphenol A type epoxy resin, phenol xenyl aralkyl-type epoxy resin and bis-phenol phenolic resin varnish type epoxy resin.They can To be used alone, can also be applied in combination with two or more.
Commercially available product can be used in these compounds.Such as it as bisphenol A diglycidyl ether, can enumerate Epikote 828, Epikote 1001 and Epikote 1002 (being Japan Epoxy Resins corporation) etc..As It is (new can to enumerate Epikote 807 (Japan Epoxy Resins corporation), YSLV-80 for Bisphenol F diglycidyl ether Day iron Chemical Co., Ltd. system) etc., as bisphenol-S diglycidyl ether, EBPS-200 (Japanese chemical drug company can be enumerated System) and EPICLON EXA-1514 (big Japanese ink chemical industrial company system) etc..In addition, as xenol 2-glycidyl Ether can enumerate YL6121 (Japan Epoxy Resins corporation) etc., can as union II cresols diglycidyl ether To enumerate YX4000H (Japan Epoxy Resins corporation) etc..It in turn, can be with as hydrogenated bisphenol A glycidol ether Enumerate ST-2004 and ST-2007 (being Dongdu chemical conversion corporation) etc..As phenol xenyl aralkyl type epoxy tree Rouge can enumerate NC-3000H (Nippon Kayaku K. K's system).They can be used alone, two or more also can be used.
Among the above, from the viewpoint of fracture resistance, bisphenol f type epoxy resin, phenol xenyl aralkyl are preferably comprised Type epoxy resin or bis-phenol phenolic resin varnish type epoxy resin.
As above-mentioned bisphenol f type epoxy resin, YSLV-80 (Nippon Steel Chemical Co., Ltd's system) etc. can be enumerated.Separately Outside, as phenol xenyl aralkyl-type epoxy resin, NC-3000H (Nippon Kayaku K. K's system) etc. can be enumerated.Into And as bis-phenol phenolic resin varnish type epoxy resin, EXA-7372 (bisphenol-f type phenolic resin varnish type epoxy resin, DIC can be obtained Co. Ltd. system), 157S70 (bisphenol A-type phenolic varnish type polyfunctional epoxy resin, Mitsubishi chemical Co., Ltd's system).They can To be used alone, two or more also can be used.
(d) content of ingredient is, 100 mass parts of total amount relative to (a) ingredient He (b) ingredient be preferably 5 mass parts~ 50 mass parts, more preferably 10 mass parts~40 mass parts, further preferably 15 mass parts~40 mass parts, particularly preferably 20 mass parts~35 mass parts.
[(e) ingredient: inorganic filler]
Photosensitive polymer combination of the invention contains inorganic filler.As (e) ingredient, can be used such as barium sulfate, Barium titanate, powdery silica, amorphous silica, talcum, clay, firing kaolin, magnesium carbonate, calcium carbonate, aluminium oxide, hydrogen Aluminium oxide, mica powder.Among the above, from the viewpoint of low CTEization, silica filler is preferably comprised.
From the HAST patience met under ultra tiny interval, CTE is reduced, from the perspective of improving clarity and gold-plated patience, Being preferably used in photosensitive polymer combination with maximum particle diameter is the silica filler that 1 μm of state below is dispersed.
In addition, inorganic filler is 1 μm of state dispersion below with maximum particle diameter preferably in photosensitive polymer combination, into And the average grain diameter of inorganic filler is preferably 3~300nm, more preferably 5~300nm.
As the type of above-mentioned silica filler, spherical silicon dioxide is melted, melting crushes silica, crystalline two Silica, smoke-like silica, sol-gel silica etc. can be used.From the viewpoint of partial size, preferred molten Spherical silicon dioxide, smoke-like silica, sol-gel silica etc., wherein more preferable smoke-like silica, colloidal sol Gel silicas.Silica is scattered in resin without cohesion with the state of primary particle size to use.At this point, can also be right Silica surface carries out silane coupled processing.
As above-mentioned silane coupling agent, the silane coupling agent for being generally possible to obtain can be used.Alkyl can be used for example Silane, alkoxy silane, vinyl silanes, epoxy silane, amino silane, acrylic silane, methacryl silanes, sulfydryl silicon Alkane, sulfidesilane, isocynate silane, sulfuric silane, styryl silane, alkylchlorosilane.
As above-mentioned silane coupling agent, can enumerate for example methyltrimethoxysilane, dimethyldimethoxysil,ne, Trimethylmethoxysilane, methyltriethoxysilane, methyl triple phenoxyl silane, ethyl trimethoxy silane, n-propyl three Methoxy silane, diisopropyl dimethoxy silane, trimethoxysilane, second, isobutyl dimethoxy silane, isobutyl Ethyl triethoxy silicane alkane, n-hexyl trimethoxy silane, n-hexyl triethoxysilane, Cyclohexyl Methyl Dimethoxysilane, N-octytriethoxysilane, n-dodecane methoxylsilane, phenyltrimethoxysila,e, dimethoxydiphenylsilane, Tri-phenyl-silane alcohol, methyl trichlorosilane, dimethyldichlorosilane, trim,ethylchlorosilane, n-octyl dimethylchlorosilane, tetrem Oxysilane, 3- TSL 8330,3-aminopropyltriethoxysilane, 3- (2- amino-ethyl) aminopropyl Trimethoxy silane, 3- (2- amino-ethyl) aminopropylmethyldimethoxysilane, 3- phenyl amino propyl trimethoxy silicon Alkane, 3- glycidoxypropyltrime,hoxysilane, 3- epoxy propoxy propyl methyl dimethoxysilane, 3- glycidoxy Propyl-triethoxysilicane, 3- glycidoxypropyl diethoxy silane, bis- (3- (triethoxysilyl) third Base) disulphide, bis- (3- (triethoxysilyl) propyl) tetrasulfides, vinyltriacetoxy silane, vinyl Trimethoxy silane, vinyltriethoxysilane, vinyl silane triisopropoxide, allyltrimethoxysilanis, diene Dimethylamine base silane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloyloxypropyl methyl diformazan Oxysilane, 3- methacryloxypropyl, 3-mercaptopropyi trimethoxy silane, 3- mercaptopropyi first Base dimethoxysilane, 3- Mercaptopropyltriethoxysilane, N- (1,3- dimethyl butyrate fork) -3- aminopropyl triethoxysilicane Alkane, amino silane.
(e) ingredient preferably contains silica and barium sulfate simultaneously.By using both silica and barium sulfate, hold Easily make it have desired particle diameter distribution, additionally it is possible to adjust the hardness of photosensitive polymer combination.
(e) content of ingredient is that 100 mass parts of total amount relative to (a) ingredient He (b) ingredient are preferably 1~100 mass Part, more preferably 5~80 mass parts, further preferably 10~50 mass parts.
The content of above-mentioned silica filler is that 100 mass parts of total amount relative to (a) ingredient He (b) ingredient are preferably 10~500 mass parts, more preferably 20~400 mass parts, further preferably 50~300 mass parts are particularly preferably more than 60 mass parts.
In addition, in addition to containing other than above-mentioned (a)~(e) ingredient in photosensitive polymer combination of the invention, preferably into One step contains polymerization inhibitor.As polymerization inhibitor, can enumerate quinhydrones, Hydroquinone monomethylether, tert-butyl catechol, pyrogallol, Phenthazine.Polymerization inhibitor is more preferably phenolic antioxidant.
Being able to suppress volatilization when the heating after developing procedure, the fusing point of above-mentioned polymerization inhibitor is preferably 100 DEG C or more, more preferably 125 DEG C or more.
In addition, from the viewpoint of it is anti-oxidant it is excellent, weight average molecular weight is preferably 300 or more, more preferably 370 or more.
In addition, from the viewpoint of with higher horizontal realization chemical reagent resistance and resistance to plating, above-mentioned photonasty tree Oil/fat composition is other than containing above-mentioned (a)~(e) ingredient, preferably further containing in the molecule with the compound of amino As curing accelerator.The curing accelerator can be with higher horizontal realization chemical reagent resistance and resistance to plating in film forming Property.
As in the molecule with amino curing accelerator, can enumerate such as dicyandiamide, melamine, guanamines with And its derivative, it can specifically enumerate dicyandiamide, melamine, acetylguanamine, benzoguanamine, melamine-phenol-good fortune Your Malin, four countries' chemical conversion industry corporation commercially available product；2MZ-AZINE,2E4MZ-AZINE,C11Z-AZINE,2MA-OK.Its In, preferably comprise melamine compound.
In addition it is possible to use triaizine compounds and its derivative, imidazoles system, thiazole system, triazole system, silane coupling agent etc. Additive kind.Ethyl diamino-S- triazine, 2,4- diamino-S- triazine, 2,4- diamino -6- two can specifically be enumerated The triazine derivatives species such as tolyl-S- triazine.
When above-mentioned photosensitive polymer combination contains above-mentioned curing accelerator, relative to the total of (a) ingredient and (b) ingredient Measuring 100 mass parts is preferably 0.1 mass parts~5 mass parts, more preferably 0.5 mass parts~5 mass parts, further preferably 1.0 mass parts~5 mass parts.
In addition, above-mentioned photosensitive polymer combination is according to requiring that assorted pigment composition can also be used.Pigment composition can To use green such as phthalocyanine blue, phthalocyanine green, iodine, dual-azo yellow, malachite green, crystal violet, titanium oxide, carbon black, naphthalene blue-black, azo The colorants such as the organic pigment of system or dyestuff.
In addition, in the range of not influencing the desired characteristic of photosensitive polymer combination, can also containing bentonite, Defoaming agent, the levelling of the thixotropy conferring agents such as montmorillonite, aerosil, amide waxe, silicone-based, fluorine system, macromolecular etc. Agent etc..
Photosensitive polymer combination of the invention also includes the form for being mixed in above-mentioned each ingredient in solvent and being formed. As solvent, alcohol, glycol ethers, ethylene glycol is can be used in the viewpoints such as easiness formed from the dissolubility of each ingredient, film Alkylether acetates, ester or diethylene glycol.
, it is preferable to use ethylene glycol monobutyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, diethyl two in above-mentioned solvent Alcohol Anaesthetie Ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetic acid esters.
In addition, content is relative to photoresist when photosensitive polymer combination used in the present invention contains solvent Total composition is preferably 5~40 mass %.
[photosensitive film]
In the following, the photosensitive film to preferred embodiment is illustrated.The photosensitive film of present embodiment is tool The photosensitive film of standby supporter and the photosensitive layer being made of above-mentioned photosensitive polymer combination being set on the support.It is photosensitive Layer is also referred to as photosensitive polymer combination layer.In addition, the guarantor for covering the photosensitive layer can also be further equipped on above-mentioned photosensitive layer Protect film.
As above-mentioned supporter, the polyester such as polyethylene terephthalate, polypropylene, polyethylene etc. can be used Thin polymer film with heat resistance and solvent resistance.The thickness of above-mentioned supporter (thin polymer film) is preferably 5~25 μm.It should When thickness is lower than 5 μm, support membrane has crackly tendency when the support film stripping carried out before development, the thickness if it exceeds 25 μm, then clarity has the tendency that decline.In addition, above-mentioned thin polymer film can also be used as supporter and protective film for a kind of Be laminated in photosensitive layer two sides come using.
As above-mentioned protective film, the polyester such as polyethylene terephthalate, polypropylene, polyethylene can be used Deng the thin polymer film with heat resistance and solvent resistance.As commercially available product, such as Oji Paper strain formula can be enumerated The polypropylene film of the product name " ア Le Off ァ Application MA-410 " of commercial firm, " E-200C ", Shin Etsu Film Co., Ltd. etc., Supreme Being Pet films such as the PS series such as the product name " PS-25 " of people's Co. Ltd. system etc., but it is not limited to this A bit.
The thickness of above-mentioned protective film is preferably 1~100 μm, more preferably 5~50 μm, further preferably 5~30 μm, Particularly preferably 15~30 μm.When the thickness is lower than 1 μm, protective film has the tendency that rupture when lamination, the thickness if it exceeds 100 μm, then has the tendency that cheapness variation.In addition, the bonding force phase for protective film, preferably between photosensitive layer and supporter Than the smaller protective film of bonding force between photosensitive layer and protective film, additionally, it is preferred that low fault (fisheye, also referred to as fish Eye) film.When fault is referred to material through the manufacture film such as heat fusing, mixing, extrusion, biaxial stretch-formed, casting, material Foreign matter, undissolved object, oxidative degradation object etc. enter in film and generate.
Above-mentioned photosensitive layer is preferably formed as follows: above-mentioned photosensitive polymer combination being dissolved in above-mentioned solvent, is made After solution (coating fluid) of the solid component for 30~70 mass % or so, which is coated on supporter and is done It is dry.Above-mentioned coating can be by using sized roller applicator, comma formula spreader, gravure coater, airblade coating device, die coating The well known method of device, rod coaters etc. carries out.In addition, above-mentioned drying can carry out 5~30 minutes left sides at 70~150 DEG C It is right.From the viewpoint of preventing organic solvent diffusion in a subsequent process step, the remaining in photosensitive polymer combination is organic molten Dosage is preferably 3 mass % or less relative to the total amount of photosensitive polymer combination.
The thickness of above-mentioned photosensitive layer difference depending on the application and it is different, it is dry after thickness be preferably 5~200 μm, it is more excellent It is selected as 15~60 μm, particularly preferably 20~50 μm.When the thickness is lower than 5 μm, have the tendency that industrial application difficulties, the thickness If it exceeds 200 μm, sensitivity and clarity inside photosensitive layer have the tendency that decline.
Above-mentioned photosensitive film can also further have buffer layer, adhesive layer, light absorbing layer, barrier layer for gases etc. intermediate Layer.In addition, obtained photosensitive film can be wound into a roll tubular with sheet or in core to take care of.Furthermore it is preferred that pressing Make supporter become outermost mode when like this to wind.From the viewpoint of the protection of end face, preferably in above-mentioned scroll-like sense End face spacer is set on the end face of photosensitiveness film roll and is preferably provided with damp proof end face spacer from the viewpoint of resistance to edge-melting. In addition, edge-melting, which refers to, is wound into a roll tubular come the phenomenon that when saving, photosensitive polymer combination is oozed out from reel end face.In addition, As packing method, preferably packed by wrapping in the small black sheet material of penetrability.As above-mentioned core, example can be enumerated Such as polyvinyl resin, acrylic resin, polystyrene resin, Corvic, ABS resin (acrylonitrile-butadiene-benzene second Alkene copolymer) etc. plastics etc..
[forming method of corrosion-resisting pattern]
In the following, being illustrated to the forming method of the corrosion-resisting pattern for the photosensitive film for having used present embodiment.
Firstly, forming the photosensitive layer being made of above-mentioned photosensitive polymer combination on the substrate of resist to be formed. Specifically, being formed in above-mentioned photosensitive film on substrate according to covering by lamination (laminate) etc. has circuit pattern Conductor layer mode carry out it is closely sealed.When above-mentioned photosensitive film has protective film on photosensitive layer, by the protective film It is removed from photosensitive film, makes the face exposed in the way of the conductor layer with circuit pattern that covering is formed on substrate It carries out closely sealed.From the viewpoint of improving adhesiveness, tracing ability, preferably make its closely sealed under reduced pressure.In addition, photoresist group Closing object can also be by method well known to silk screen print method or the method being coated using sized roller applicator etc. by photoresist group The varnish for closing object is coated on substrate.
Then, it carries out following exposure process: through mask pattern, active ray being irradiated to the prescribed portion of photosensitive layer, Make the photosensitive layer photocuring of irradiation portion, forms photocuring portion.
In turn, when there are when supporter, after removing the supporter, passing through wet developing on photosensitive layer or dry process development remove The part (unexposed portion) of non-photocuring is simultaneously developed, it is possible thereby to form corrosion-resisting pattern.
In the case where above-mentioned wet developing, as developer solution, alkaline water is used according to the type of photosensitive polymer combination Solution, water system developer solution, organic solvent etc. be safe and stable, the good developer solution of operability.
As developer solution, preferably alkaline aqueous solution.As the alkali of alkaline aqueous solution, use is safe and stable, operability is good Good alkali.Such as hydroxide i.e. lithium hydroxide, sodium hydroxide, the potassium hydroxide of the alkali metal such as lithium, sodium, potassium can be enumerated Deng；Carbonate or bicarbonate, that is, alkali carbonate, ammonium carbonate or alkali metal hydrogencarbonate of alkali metal or ammonium etc. etc.；Alkali Phosphate, that is, sodium phosphate of metal, potassium phosphate etc.；Pyrophosphate, that is, sodium pyrophosphate of alkali metal, potassium pyrophosphate etc..
As aqueous alkali, the preferably such as weak solution of 0.1~5 mass % sodium carbonate, 0.1~5 mass % potassium carbonate Weak solution, the weak solution of 0.1~5 mass % sodium hydroxide, the weak solution of 0.1~5 mass % sodium tetraborate, pH are preferably set For 9~11 range.In addition, the temperature of such alkaline aqueous solution is adjusted according to the developability of photosensitive layer, it is preferably set to 20~50 DEG C.In turn, it is a small amount of that surfactant, defoaming agent etc. can also be mixed into order to promote to develop, in above-mentioned alkaline aqueous solution Organic solvent.
As above-mentioned water system developer solution, it can be used and be made of water and alkaline aqueous solution or more than one organic solvent Water system developer solution.Here, as the alkali of alkaline aqueous solution, other than above-mentioned alkali, such as borax, inclined silicon can also be enumerated Sour sodium, tetramethyl ammonium hydroxide, ethanol amine, ethylenediamine, diethylenetriamines, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3- diamino-propanol -2, morpholine.The pH of such water system developer solution is preferably in the range of development treatment can be carried out sufficiently Reduce as best one can, preferably pH is 8~12, and more preferable pH is 9~10.
As above-mentioned organic solvent, using such as acetone, ethyl acetate, the alkoxy for carbon atom number being 1~4 alkane Ethoxy-ethanol, ethyl alcohol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1,1,1- trichloroethanes, N-Methyl pyrrolidone, n,N-Dimethylformamide, cyclohexanone, methyl iso-butyl ketone (MIBK), gamma-butyrolacton. The concentration of such organic solvent is preferably generally 2~90 mass %.In addition, the temperature of such organic solvent can be according to aobvious Shadow is adjusted.In addition, such organic solvent can be used alone, can also be used with two kinds of combination of the above.As individually making Organic solvent system developer solution, can enumerate such as 1,1,1- trichloroethanes, N-Methyl pyrrolidone, N, N- dimethyl methyl Amide, cyclohexanone, methyl iso-butyl ketone (MIBK), gamma-butyrolacton.
As the developing method of corrosion-resisting pattern, impregnation method, sheathed submergence mode, spray regime, high pressure can be enumerated Spray regime, brushing, slap (slapping) etc., high-pressure injection mode are most suitable for clarity raising.It is against corrosion In the forming method of pattern, two kinds or more above-mentioned of developing method also can be used together as needed.The metal carried out after development The etching in face can be used such as copper chloride solution, ferric chloride solution, alkaline etching etching solution.
[permanent resist]
The preferred embodiment for the permanent resist for having used above-mentioned photosensitive film is illustrated below.
After above-mentioned developing procedure, in order to improve scolding tin heat resistance and chemical reagent resistance etc., high pressure water is preferably used Silver-colored lamp carries out ultraviolet light irradiation or heating.In the case where irradiating ultraviolet light, it can according to need and adjust its exposure, such as can With with 0.05~10J/cm2The exposure of left and right is irradiated.In addition, in the case where heating corrosion-resisting pattern, preferably 130~ It is carried out 15~90 minutes or so in the range of 200 DEG C or so.
Both ultraviolet light irradiation and heating can also carry out.At this point it is possible to which the two carries out simultaneously, also can be implemented any Person implements another one again later.At the same time carry out ultraviolet light irradiation and heating when, from more well assign scolding tin heat resistance with And from the perspective of chemical reagent resistance, it is preferably heated to 60~150 DEG C.
The permanent resist being formed as described above can be as the protective film of the wiring after the implementation soldering on substrate, tool There are the various characteristics of solder resist, can be used as printed wiring board purposes, conductor package substrate purposes, flexible distributing board Solder resist uses.
Above-mentioned solder resist is in addition to for example when implementing plating or etching to substrate, can be used as plating resist or etching Except resist (also referred to as underseal) use, it can also remain on substrate as former state, the protective film as protection wiring etc. (permanent resist) uses.
In addition, making the prescribed portion of above-mentioned conductor layer as unexposed figure using having in above-mentioned exposure process The mask or describing data of case when being exposed, remove unexposed portion and being developed, and obtain being formed on substrate Conductor layer a part expose, resist with patterns of openings.Then, it is above-mentioned to be formed preferably to carry out necessary processing Permanent resist.
[semiconductor packages]
The photosensitive polymer combination of present embodiment can be suitably used for semiconductor package type printed wiring board forever The formation of long resist film.That is, the present invention provide it is a kind of with being made of the solidfied material of above-mentioned photosensitive polymer combination The semiconductor packages of permanent resist layer.Fig. 1 is the schematic section for indicating an embodiment of semiconductor packages.Semiconductor package It fills 10 and has substrate for mounting semiconductor chip 50, the semiconductor chip being mounted on substrate for mounting semiconductor chip 50 120. The bonding agent 117 that substrate for mounting semiconductor chip 50 and the die-bonding film of semiconductor chip 120 or chip solder paste are constituted Bonding.Substrate for mounting semiconductor chip 50 has insulating substrate 100, is provided with lead on a face of insulating substrate 100 The permanent resist layer 90 for the opening portion that engagement wiring terminals 110, a part for being formed with wiring terminals 110 are exposed, in phase Permanent resist layer 90 is provided on the face tossed about to be connected with scolding tin with connection terminal 111.Permanent resist layer 90 is by above-mentioned The layer that the solidfied material of the photosensitive polymer combination of present embodiment is constituted.Scolding tin connection is with connection terminal 111 equipped with soldered ball 114, it is electrically connected for carrying out with printed wiring board.Semiconductor chip 120 and wire bonding use metal with wiring terminals 110 Line 115 is electrically connected.Semiconductor chip 120 is sealed by semiconductor sealing resin 116.In addition, the photonasty of present embodiment Resin combination can be applicable to the semiconductor packages of flip-chip type.
Fig. 2 is the schematic section for indicating the conductor package substrate of flip-chip type.The semiconductor packages base of flip-chip type The semiconductor chip that plate 20 has substrate for mounting semiconductor chip 50 and is mounted on substrate for mounting semiconductor chip 50 120.Substrate for mounting semiconductor chip 50 and semiconductor chip 120 are filled by bottom filler 118.Semiconductor-chip-mounting is used Substrate 50 has the composition being laminated according to the sequence of insulating substrate 100b, insulating substrate 100a and permanent resist layer 90.Permanently Resist layer 90 is the layer being made of the solidfied material of the photosensitive polymer combination of above-mentioned present embodiment.Insulating substrate 100b exists The surface of the side insulating substrate 100a has the thin copper film 80 being patterned, table of the insulating substrate 100a in permanent 90 side of resist layer Face has the thin copper film 80 being patterned.The thin copper film 80 on thin copper film 80 and insulating substrate 100a on insulating substrate 100b At least part is connected the scolding tin formed in a manner of penetrating through insulating substrate 100a and insulating substrate 100b uses connection terminal 111 electrical connections.In addition, permanent resist layer 90 is formed in a manner of covering the thin copper film 80 on insulating substrate 100a, with weldering On the tin connection corresponding thin copper film 80 of connection terminal 111, opening portion 112 is formed in a manner of exposing thin copper film 80.Insulation Thin copper film 80 on substrate 100a on the face opposite with substrate for mounting semiconductor chip 50 for being formed in semiconductor chip 120 Thin copper film 80 be electrically connected by the soldered ball 114 that is arranged on above-mentioned opening portion 112.
It is installed on the electronic equipments such as PC after the substrate for having permanent resist.
More than, it is described the invention in detail according to embodiments thereof.But the present invention is not by above embodiment Limitation, various modifications can be carried out in the range without departing from its main idea.
The present invention, which for example could also say that, is related to the invention of the application of above-mentioned photosensitive polymer combination.That is, of the invention It is a kind of application of photosensitive polymer combination in the manufacture of photosensitive film, the photosensitive polymer combination on one side Contain (a) ingredient: sour modified epoxy, (b) ingredient: with the photopolymerization monomers of ethylenically unsaturated groups, (c) at Point: Photoepolymerizationinitiater initiater, (d) ingredient: epoxy resin and (e) ingredient: inorganic filler, it is modified double that above-mentioned (a) ingredient contains acid Phenol phenolic resin varnish type epoxy resin, and then meet at least one condition of following (I) and (II) expression.
(I) described (b) ingredient contains the photopolymerization monomer with tristane structure and urethane bond.
(II) 100 mass parts of total amount relative to (a) ingredient and (b) ingredient, (e) ingredient, which contains, to be had more than 60 parts of maximum particle diameter is 1 μm of silica filler below.
In addition, another aspect of the present invention is a kind of photosensitive polymer combination as permanent resist manufacture photonasty The application of resin combination, the photosensitive polymer combination contain (a) ingredient: sour modified epoxy, (b) ingredient: having Photopolymerization monomer, (c) ingredient of ethylenically unsaturated groups: Photoepolymerizationinitiater initiater, (d) ingredient: epoxy resin and (e) Ingredient: inorganic filler, above-mentioned (a) ingredient contain sour modified bisphenol phenolic resin varnish type epoxy resin, so meet above-mentioned (I) and (II) at least one condition indicated.
In addition, another aspect of the present invention is a kind of solidfied material of photosensitive polymer combination in permanent resist Using the photosensitive polymer combination contains (a) ingredient: sour modified epoxy, (b) ingredient: having ethylenic bond unsaturated Photopolymerization monomer, (c) ingredient of group: Photoepolymerizationinitiater initiater, (d) ingredient: epoxy resin and (e) ingredient: inorganic to fill out Material, above-mentioned (a) ingredient contain sour modified bisphenol phenolic resin varnish type epoxy resin, and then meet above-mentioned (I) and (II) expression extremely A few condition.
Embodiment
In the following, being more specifically illustrated by embodiment to the present invention, but the present invention is not restricted by the embodiments.
(production of photosensitive film)
Each ingredient shown in table 1~3 is mixed according to match ratio shown in table (quality criteria), obtains embodiment 1 ~16, the photosensitive polymer combination of comparative example 1~15.In addition, solvent uses methyl ethyl ketone.
As each ingredient shown in table 1~3, following ingredients is used.
[(a) ingredient]
EXP-3133: bisphenol F phenolic varnish type acid modified epoxy (weight average molecular weight 7000, acid value 63mgKOH/g, Dainippon Ink Chemicals's system)
EXP-3135: bisphenol F phenolic varnish type acid modified epoxy (weight average molecular weight 8000, acid value 75mgKOH/g, Dainippon Ink Chemicals's system)
EXP-2810: first rank phenolic varnish type acid modified epoxy acrylic ester (weight average molecular weight 7000, acid value 65mgKOH/ G, Dainippon Ink Chemicals's system)
ZFR-1158: bisphenol-f type acid modified epoxy acrylic ester (weight average molecular weight 10000, acid value 65mgKOH/g, Japan Chemical drug Co. Ltd. system)
UXE-3024: urethane-modified bisphenol A-type acid modified epoxy acrylic ester (weight average molecular weight 10000, acid value 67mgKOH/g, Nippon Kayaku K. K's system)
[measuring method of acid value]
Acid value measures as described below.Firstly, binder polymer is heated 1 hour at 130 DEG C, removing is volatilized into Point, obtain solid component.Then, accurate weighing will measure the polymer 1g of acid value, and acetone then is added in the polymer 30g, by its uniform dissolution.Then, suitable indicator phenolphthalein is added in the solution, is carried out using the KOH aqueous solution of 0.1N Titration.Then, acid value is calculated by following formula.
Acid value=10 × Vf × 56.1/ (Wp × I)
In formula, Vf indicates that the titer (mL) of phenolphthalein, Wp indicate the weight (g) of the binder polymer solution of measurement, I table Show the ratio (quality %) of the nonvolatile component in the binder polymer solution of measurement.
[measurement of weight average molecular weight]
In addition, weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC), the school of standard polystyren is used Directrix curve is exported by conversion.The condition of GPC is as follows.
GPC condition
Pump: Hitachi's L-6000 type (Hitachi Co., Ltd's system, product name)
Chromatographic column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (are by Hitachi above At Industrial Co., Ltd's system, product name)
Elutriant: tetrahydrofuran
Measuring temperature: 40 DEG C
Flow: 2.05mL/ minutes
Detector: Hitachi L-3300 type RI (Hitachi Co., Ltd's system, product name)
[(b) ingredient]
UX-5002D-M20: urethane acrylate (weight average molecular weight 3500, Japan containing tristane structure Chemical drug Co. Ltd. system)
UX-5002D-P20: urethane acrylate (weight average molecular weight 3500, Japan containing tristane structure Chemical drug Co. Ltd. system)
NK-DCP: Tricyclodecane Dimethanol dimethylacrylate (weight average molecular weight 332, the village Xin Zhong chemical industry strain formula Commercial firm's system)
DPHA: dipentaerythritol hexaacrylate (weight average molecular weight 578, Nippon Kayaku K. K's system)
FA-321M: bisphenol A polyethenoxy dimethylacrylate (weight average molecular weight 836, Hitachi's chemical conversion industry strain formula meeting Society's system)
[(c) ingredient]
I-907:2- methyl-1-(4- methyl mercapto phenyl)-2- morpholino propane-1- ketone (IRGACURE-907, BASF plants of formulas Commercial firm's system)
DETX-S:2,4- diethyl thioxanthone (KAYACURE-DETX-S, Nippon Kayaku K. K's system)
TPO:2,4,6- trimethylbenzoy-diphenies-phosphine oxide (LUCIRIN-TPO, BASF Co. Ltd. system)
OXE-02: ethyl ketone, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -, 1- (O- acetyl oxime) (IRGACURE-OXE-02, BASF Co. Ltd. system)
[(d) ingredient]
EXA-7372: bisphenol F phenolic type epoxy resin (Dainippon Ink Chemicals's system)
NC-3000H: phenol xenyl aralkyl-type epoxy resin (Nippon Kayaku K. K's system)
YSLV-80: bisphenol f type epoxy resin (Nippon Steel Chemical Co., Ltd's system)
[(e) ingredient]
Silica filler A: prepare silica filler average grain diameter be 100nm, and as silane coupling agent and 3- methacryloxypropyl trimethoxy silane used as methacryl base silane has carried out the two of coupling processing Cilicon oxide filler.It is scattered in the resin of (a) ingredient and is used.Dispersity uses laser diffraction formula Microtrac Distribution instrument HRA-X100 (day machine fills corporation) is spent to measure, and as a result average grain diameter is 50nm, maximum particle diameter 204nm.In addition, Evaluation is all measured in the same manner as described above measurement every time, as a result confirms, be average grain diameter is 100nm hereinafter, maximum particle diameter is 1 μm Below.
Silica filler B: the crystallization that the average grain diameter for preparing silica filler is 800nm is crushed silica.It will It is scattered in resin (a) to use with 3 rollers.Dispersity uses laser diffraction formula Microtrac particles distribution instrument HRA- X100 (Ji Zhuan society system) is measured, and as a result average grain diameter is 546nm, and maximum particle diameter is 3.8 μm.In addition, every time evaluation all with It is above-mentioned to be carried out similarly measurement, as a result confirm, be average grain diameter is 800nm hereinafter, maximum particle diameter is 5 μm or less.
Barium sulfate: as filler, prepare the barium sulfate that average grain diameter is 200 μm.By it according to method tune as shown below Dispersion liquid is made and uses.In relation to ethylenically unsaturated groups photopolymerization monomer (above-mentioned (b) ingredient and/or with (b) Ingredient difference person), barium sulfate, melamine and methyl ethyl ketone, in Star Mill LMZ (Finetech plants of formula meetings of Ashizawa Society's system) in the amount recorded in input table 1 or 2, the zirconium oxide bead for the use of diameter being 1.0mm divides under 12m/ second peripheral speeds It dissipates 3 hours, modulates barium sulfate dispersion liquid.
■ aluminium oxide (alumina): average grain diameter is the methyl iso-butyl ketone (MIBK) dispersed paste of the aluminium oxide of 50nm (ALMMIBK-H06, CIK NanoTek Co. Ltd. system)
[other ingredients]
Polymerization inhibitor: AW-300, Kawaguchi's chemical industry Co. Ltd. system, weight average molecular weight 380,205 DEG C of fusing point
Dicyandiamide: Mitsubishi chemical Co., Ltd's system
Melamine: Nissan Chemical Ind Ltd's system
Pigment: HCP-PM-5385, Toyo Ink Co., Ltd.'s system
Phthalocyanine blue: Japanese Pigment Co. Ltd. system
Using above-mentioned each ingredient, photosensitive polymer combination solution is modulated under conditions of record in table 1~3.Then, The photosensitive polymer combination solution of modulation is spread evenly across to the polyethylene terephthalate of 16 μ m-thicks as supporting layer On ester film (G2-16, Teijin Ltd's system), photosensitive layer is formed, is done it at 100 DEG C using hot wind convection type drying machine Dry about 10 minutes.Film thickness after the drying of photosensitive layer is 25 μm.
Then, be bonded on the surface of the opposite side of the supporting layer of photosensitive layer contact side polyethylene film (NF-15, TAMAPOLY Co. Ltd. system) it is used as protective film, obtain that there is supporting layer/photosensitive layer/protective film photosensitive film.
Table 1
Table 2
Table 3
(evaluating characteristics)
[evaluation for applying film property]
The pet film of photosensitive film is removed without exposing to obtained photosensitive film, is used Finger gently presses its film coated surface, according to following benchmark evaluation to the level of adhesion of finger.That is, not finding, not finding opponent substantially The adhesion of finger slightly finds being denoted as " 3 " to the adhesion of finger, finds being denoted as " 2 " for the adhesion to finger, discovery resin is attached On finger this degree adhere by force be denoted as " 1 ".As a result it is shown in table 4~6.
[evaluation of clarity]
Printed wiring board base obtained from the copper foil of 12 μ m-thicks has been laminated on glass epoxide substrate with the grinding of abrasive grain brush The copper surface of plate (E-679, Hitachi Chemical Co., Ltd.'s system), after washing, is dried.In the printed wiring board substrate On, it is 70 in compacting hot plate temperature using continuous pressing type vacuum laminator (MVLP-500, Co., Ltd. Mingji Koito's system) DEG C, the pumpdown time be 20 seconds, the lamination pressing time is 30 seconds, the condition that it is 0.4MPa that air pressure, which is 4kPa or less, is pressing against pressure The lower polyethylene film for removing above-mentioned photosensitive film and stacking obtain evaluation stacking structure base board.
In above-mentioned evaluation on stacking structure base board, adhering to has the photomask of the pattern of 2mm square as egative film, uses strain Formula commercial firm オ ー Network makes made EXM-1201 type exposure machine, according to the remaining after the development for making Stouffer21 grades of ladder tables The energy fluence that ladder series is 8.0 is exposed.Then, after standing 1 hour under room temperature (25 DEG C), above-mentioned evaluation layer is removed Pet film on stack substrate is developed in 30 DEG C of 1 mass % aqueous sodium carbonate with minimum 2.0 times of the time of time (the developed minimum time in unexposed portion) carries out spray developing, forms pattern.
As the evaluation of clarity at this time, 30 μm of φ of unexposed portion is developed and obtains as good resist shape Being denoted as " 3 " for patterns of openings was obtained, resist shape is despite overhanging shape (overhang) but has obtained being denoted as patterns of openings " 2 ", do not obtain patterns of openings is denoted as " 1 ".As a result it is shown in table 4~6.
[evaluation of gold-plated patience]
Using commercially available non-electrolytic ni au plating liquid, according to the side for making 5 μm of nickel coating thickness, gold plate thickness is 0.1 μm Formula carries out plating with stacking structure base board to the evaluation of the above-mentioned solder resist for foring the opening portion with 2mm square, uses The appearance of entity microscope observing solder resist, is evaluated according to following benchmark.Resist that is, solder is can't see on opening portion periphery The albefaction for losing agent is denoted as " 3 ", has 10 μm of albefactions below and that is removed be denoted as " 2 ", albefaction, removing occur significantly Be denoted as " 1 ".As a result it is shown in table 4~6.
[evaluation of Tg, CTE]
The whole face of above-mentioned photosensitive film is exposed, is then developed, ultraviolet light irradiation, heat treatment, thus Consolidating for solder resist is formed on the pet film (G2-16, Teijin Ltd's system) of 16 μ m-thicks Then compound after being cut into wide 3mm, long 30mm with cutter, removes the polyethylene terephthalate of the photosensitive film Ester obtains thermal expansion coefficient evaluation photoresist solidfied material.Use TMA device SS6000 (セ イ コ ー イ Application ス Star Le メ Application Le Co. Ltd. system), measure the thermal expansion coefficient under stretch mode.Stretching loading is 2g, span (distance between collet) For 15mm, heating rate is 10 DEG C/min.Firstly, sample is installed on device, 160 DEG C are heated to from room temperature (25 DEG C), is put It sets 15 minutes.It is then cooled to -60 DEG C, under conditions of being warming up to 250 DEG C from -60 DEG C with 10 DEG C/min of heating rate into Row measurement.The inflection point seen in the range of from 25 DEG C to 200 DEG C is set as Tg, temperature at this time is 120 DEG C or more and is denoted as " 3 " below are denoted as " 1 " for 100 DEG C to be denoted as " 2 " more than or equal to 100 DEG C and lower than 120 DEG C.CTE use is in Tg or less At a temperature of the obtained slope of curve near tangent.The value of CTE obtained in embodiment 1 is set as a reference value, relative to this A reference value be 70% it is below be denoted as " 4 ", being denoted as " 3 " more than 70% but lower than 130%, 130% or more but lower than 150% It is denoted as " 2 ", 150% or more is denoted as " 1 ".As a result it is shown in table 4~6.
[evaluation of HAST patience]
As core material, the printed wiring board substrate for the copper foil that 12 μ m-thicks are laminated on glass epoxide substrate is used (MCL-E-679FG, Hitachi Chemical Co., Ltd.), half addition (Japanese original text are as follows: セ ミ ア デ ィ Block) wiring are formed with product Layer material (AS-ZII, Hitachi Chemical Co., Ltd.'s system), 8 μm/8 μm of production line width/be divided into of comb-type electrode, is set To evaluate substrate.On the comb-type electrode of the evaluation substrate, it is identically formed with above-mentioned " evaluation of clarity " by resist The solder resist that solidfied material is constituted (is exposed in the way of making on comb-type electrode part remaining solder resist, and is shown Shadow, heats to be formed at ultraviolet light irradiation), then, in the environment of 130 DEG C, 85%RH, in the shape for the voltage for applying 6V Exposure 200 hours under state.Then, the degree for measuring resistance value and the generation with the migration of 100 times of metal microstructure sem observation, according to Following benchmark are evaluated.That is, resistance value is maintained at 1.0 × 1010Ω or more, and do not migrated on solder resist film Be denoted as " 3 ", resistance value is maintained at 1.0 × 1010Ω or more, but being denoted as " 2 " for little by little migration has occurred, resistance value becomes small In 1.0 × 1010Ω, and migrate substantially occur be denoted as " 1 ".As a result it is shown in table 4~6.
[evaluation of fracture patience]
Use stacking structure base board -65 the evaluation for being identically formed solder resist with above-mentioned " production of evaluation substrate " DEG C air in after exposure 15 minutes, heated up with 180 DEG C/min of heating rate, then, the exposure 15 in 150 DEG C of air After minute, cooled down with 180 DEG C/min of cooling rate, above-mentioned thermal cycle is repeated 1000 times.It is sudden and violent under above-mentioned environment After dew, the fracture and extent of exfoliation of the permanent resist film of stacking structure base board are used with 100 times of metal microstructure sem observation evaluation, It is evaluated according to following benchmark.That is, confirming the opening portion of 2mm square at 10 and not observing the disconnected of permanent resist film completely Split and that removes be denoted as " 3 ", at 10 in have and observe being denoted as " 2 " for fracture and removing at 2 under, at 10 in have more than at 3 and see Observe fracture and removing is denoted as " 1 ".As a result it is shown in table 4~6.
Table 4
Table 5
Table 6
Possibility is utilized in industry
According to the present invention it is possible to provide fracture patience in a kind of CTE low, Tg high and high multilager base plate it is excellent and The photosensitive polymer combination of the excellent solder resist for capableing of alkali development of HAST patience under ultra micro thin space and make With the photosensitive film of the photosensitive composite.
Symbol description
10: semiconductor packages, 20: flip-chip semiconductor encapsulation, 50: substrate for mounting semiconductor chip, 80: copper cloth Line, 90: permanent resist layer, 100a, b: insulating substrate, 110: wire bonding wiring terminals, 111: scolding tin connection connection Terminal, 112: opening portion, 114: soldered ball, 115: metal wire, 116: semiconductor sealing resin, 117: bonding agent, 118: bottom Filler, 120: semiconductor chip.

Claims (52)

1. a kind of photosensitive polymer combination, contains:
(a) ingredient: sour modified epoxy,
(b) ingredient: with ethylenically unsaturated groups photopolymerization monomer,
(c) ingredient: Photoepolymerizationinitiater initiater,
(d) ingredient: epoxy resin and
(e) ingredient: inorganic filler,
Wherein, (a) ingredient contains sour modified bisphenol phenolic resin varnish type epoxy resin,
The photosensitive polymer combination is for manufacturing permanent resist.
2. photosensitive polymer combination according to claim 1, wherein (b) ingredient contains with tristane knot The photopolymerization monomer of structure and urethane bond.
3. photosensitive polymer combination according to claim 1 or 2, wherein (e) ingredient relative to (a) at Divide and 100 mass parts of total amount of (b) ingredient are filled out containing the maximum particle diameter for having more than 60 mass parts for 1 μm of silica below Material.
4. photosensitive polymer combination according to claim 1 or 2, wherein the acid modified bisphenol novolaks type ring Oxygen resin contains sour modified bisphenol F phenolic resin varnish type epoxy resin.
5. photosensitive polymer combination according to claim 1 or 2, wherein the acid modified bisphenol novolaks type ring Oxygen resin contains acid modified bisphenol phenolic resin varnish type epoxy resin obtained from making multi-anhydride and carboxylate addition, the esterification Object is the ester that the epoxy resin for the structure that there is the following general formula (1) to indicate is formed with the monocarboxylic acid containing ethylenically unsaturated groups Compound,
In formula (1), R1Indicate hydrogen atom or glycidyl, R2Indicate hydrogen atom or methyl, n indicates 1 or more, in addition, multiple deposit R1And R2Respectively it may be the same or different.
6. photosensitive polymer combination according to claim 2, wherein described that there is tristane structure and carbamic acid The photopolymerization monomer of ester bond contains the photopolymerization monomer of the part-structure with the following general formula (2) or general formula (3) expression,
In formula (2) or formula (3), R3、R4、R5And R6Indicate Direct Bonding, alkylidene or arlydene.
7. photosensitive polymer combination according to claim 6, wherein the alkylidene in the formula (2) or (3) is The alkylidene that carbon atom number is 2~20.
8. photosensitive polymer combination according to claim 6, wherein the alkylidene in the formula (2) or (3) is The alkylidene that carbon atom number is 2~10.
9. photosensitive polymer combination according to claim 6, wherein the alkylidene in the formula (2) or (3) is The alkylidene that carbon atom number is 2~6.
10. photosensitive polymer combination according to claim 6, wherein the alkylidene in the formula (2) or (3) It is ethylidene or isopropylidene.
11. photosensitive polymer combination according to claim 6, wherein the alkylidene in the formula (2) or (3) It is ethylidene.
12. photosensitive polymer combination according to claim 6, wherein the arlydene in the formula (2) or (3) It is the arlydene that carbon atom number is 6~14.
13. photosensitive polymer combination according to claim 6, wherein the arlydene in the formula (2) or (3) It is the arlydene that carbon atom number is 6~10.
14. photosensitive polymer combination according to claim 2, wherein described that there is tristane structure and amino first The photopolymerization monomer of acid esters key contains the diol compound for making to have tristane structure, diisocyanate cpd and has Carbamate compounds obtained from the reaction of the compound of ethylenically unsaturated groups and hydroxyl.
15. photosensitive polymer combination according to claim 14, wherein the diisocyanate cpd, which contains, to be had The compound of ring structure.
16. photosensitive polymer combination according to claim 14, wherein the diisocyanate cpd contains different Buddhist That ketone diisocyanate.
17. photosensitive polymer combination according to claim 14, wherein described that there is ethylenically unsaturated groups and hydroxyl The compound of base has 2 ethylenically unsaturated groups.
18. photosensitive polymer combination according to claim 14, wherein described that there is ethylenically unsaturated groups and hydroxyl The compound of base has 3 ethylenically unsaturated groups.
19. photosensitive polymer combination according to claim 14, wherein described that there is ethylenically unsaturated groups and hydroxyl The compound of base contains the compound indicated by the following general formula (5),
In formula (5), multiple R7And R8It respectively may be the same or different, R7Indicate that carbon atom number is 1~10 Asia The arlydene that alkyl or carbon atom number are 6~14, R8The alkyl or carbon atom number that expression hydrogen atom, carbon atom number are 1~10 are 6 ~14 aryl, l, m and n indicate 1~10.
20. photosensitive polymer combination according to claim 2, wherein (b) ingredient further contains with 3 The photo polymerization monomer of above ethylenically unsaturated groups.
21. photosensitive polymer combination according to claim 20, wherein described that there is 3 or more ethylenic bond insatiable hungers With the photo polymerization monomer of group contain from the skeleton from pentaerythrite (methyl) acrylate compounds, have come from (methyl) acrylate compounds of the skeleton of dipentaerythritol and (methyl) with the skeleton from trimethylolpropane What is selected in acrylate compounds is at least one kind of.
22. photosensitive polymer combination according to claim 20, wherein described that there is 3 or more ethylenic bond insatiable hungers Contain with the photo polymerization monomer of group from (methyl) acrylate compounds and tool with the skeleton from dipentaerythritol It is selected in (methyl) acrylate compounds for having the skeleton from trimethylolpropane at least one kind of.
23. photosensitive polymer combination according to claim 20, wherein described that there is 3 or more ethylenic bond insatiable hungers Contain (methyl) acrylate compounds with the skeleton from dipentaerythritol with the photo polymerization monomer of group.
24. photosensitive polymer combination according to claim 2, wherein (b) ingredient further contains with 2 The photo polymerization monomer of ethylenically unsaturated groups.
25. photosensitive polymer combination according to claim 24, wherein described that there are 2 ethylenically unsaturated groups Photo polymerization monomer contain (methyl) acrylate of dihydroxymethyl tristane two or tristane glycol two (methyl) acrylic acid Ester.
26. photosensitive polymer combination according to claim 24, wherein described that there are 2 ethylenically unsaturated groups Photo polymerization monomer contain bisphenol-A system (methyl) acrylate compounds.
27. photosensitive polymer combination according to claim 1 or 2, wherein (c) ingredient contains aromatic ketone, oxime Ester compounds, thioxanthone compounds or acylphosphine oxide compound.
28. photosensitive polymer combination according to claim 1 or 2, wherein (c) ingredient contain aromatic ketone or Thioxanthone compounds.
29. photosensitive polymer combination according to claim 1 or 2, wherein (c) ingredient contain aromatic ketone and Thioxanthone compounds.
30. photosensitive polymer combination according to claim 1 or 2, wherein the content of (c) ingredient is relative to institute 100 mass parts of total amount for stating (a) ingredient and (b) ingredient are 0.1 mass parts~10 mass parts.
31. photosensitive polymer combination according to claim 1 or 2, wherein the content of (c) ingredient is relative to institute 100 mass parts of total amount for stating (a) ingredient and (b) ingredient are 0.5 mass parts~7 mass parts.
32. photosensitive polymer combination according to claim 1 or 2, wherein (d) ingredient contains bisphenol F type epoxy Resin, phenol xenyl aralkyl-type epoxy resin or bis-phenol phenolic resin varnish type epoxy resin.
33. photosensitive polymer combination according to claim 1 or 2, wherein the content of (d) ingredient is relative to institute 100 mass parts of total amount for stating (a) ingredient and (b) ingredient are 5 mass parts~50 mass parts.
34. photosensitive polymer combination according to claim 1 or 2, wherein the content of (d) ingredient is relative to institute 100 mass parts of total amount for stating (a) ingredient and (b) ingredient are 10 mass parts~40 mass parts.
35. photosensitive polymer combination according to claim 1 or 2, wherein the content of (d) ingredient is relative to institute 100 mass parts of total amount for stating (a) ingredient and (b) ingredient are 15 mass parts~40 mass parts.
36. photosensitive polymer combination according to claim 1 or 2, wherein the content of (d) ingredient is relative to institute 100 mass parts of total amount for stating (a) ingredient and (b) ingredient are 20 mass parts~35 mass parts.
37. photosensitive polymer combination according to claim 1 or 2, wherein (e) ingredient is in photoresist group It closes in object with maximum particle diameter as 1 μm of state dispersion below.
38. photosensitive polymer combination according to claim 1 or 2, wherein (e) ingredient contain silica and Barium sulfate.
39. photosensitive polymer combination according to claim 1 or 2, wherein it further contains polymerization inhibitor.
40. photosensitive polymer combination according to claim 39, wherein the polymerization inhibitor contains phenolic antioxidant.
41. photosensitive polymer combination according to claim 39, wherein the fusing point of the polymerization inhibitor is 100 DEG C or more.
42. photosensitive polymer combination according to claim 39, wherein the fusing point of the polymerization inhibitor is 125 DEG C or more.
43. photosensitive polymer combination according to claim 39, wherein the weight average molecular weight of the polymerization inhibitor is 300 More than.
44. photosensitive polymer combination according to claim 39, wherein the weight average molecular weight of the polymerization inhibitor is 370 More than.
45. photosensitive polymer combination according to claim 1 or 2, further contain has amino in the molecule Curing accelerator.
46. photosensitive polymer combination according to claim 45, wherein the curing accelerator contains melamine amination Close object.
47. photosensitive polymer combination according to claim 45, wherein the content of the curing accelerator is relative to institute 100 mass parts of total amount for stating (a) ingredient and (b) ingredient are 0.1 mass parts~5 mass parts.
48. photosensitive polymer combination according to claim 45, wherein the content of the curing accelerator is relative to institute 100 mass parts of total amount for stating (a) ingredient and (b) ingredient are 0.5 mass parts~5 mass parts.
49. photosensitive polymer combination according to claim 45, wherein the content of the curing accelerator is relative to institute 100 mass parts of total amount for stating (a) ingredient and (b) ingredient are 1.0 mass parts~5 mass parts.
50. a kind of photosensitive film, the photosensitive layer for having supporter and being set on the supporter, the photosensitive layer is by weighing Benefit require any one of 1~49 described in photosensitive polymer combination constitute.
51. a kind of manufacturing method of permanent resist, has following processes:
The work for the photosensitive layer that the photosensitive polymer combination described in any one of Claims 1 to 49 is constituted is set on substrate Sequence,
To the photosensitive layer with pattern-like irradiation active ray process and
The process for making the photosensitive layer develop and forming permanent resist.
52. a kind of permanent resist, the solidfied material of the photosensitive polymer combination as described in any one of Claims 1 to 49 It constitutes.
CN201910193891.XA 2011-08-10 2012-08-09 The manufacturing method of photosensitive polymer combination, photosensitive film, permanent resist and permanent resist Pending CN110083010A (en)

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